1 Enhanced Rate Chemical Processing Using Non-equilibrium Reactions Controlled with High Speed Gas Analysis IFPAC 2004 Presentation January 14, 2004 Ronald R. Rich, President Atmosphere Recovery, Inc nd Avenue North, Suite 110 Plymouth, MN Ph: (763) Fax: (763) Web:

2 Company Background  Founded Dana Corporation & DOE R&D  Heat Treating Furnace Processes  Grant & Contract Funding  Process Gas Recycling System Development  Laser Raman Gas Analyzer & Gas Processing Development  – Analyzer/Controller Field Trials  – Furnace Analyzer Offerings  – Bio-Pharma Analyzer Offerings

Manufacturing Process Goals – General  Lower Production Costs  Higher Productivity and Yields  Improved Quality  Capital Avoidance  Reduced Feedstock & Energy Use  Other Factors  New Processes & Materials  Lower Analyzer Cost of Operation  Reduced Process Air Emissions  12 Month Payback (Max.)

4 Process Gas Conceptual Needs – Better Control, Less Use Fixed Flow or Single Gas High Use (H) Std. Multi-Gas Adds Control Med. Use (M) Complete Gas Control/Reuse Low Use (L) Gas- Based Process Reactor Natural Gas and Liquid Fuels Process Gases and Liquids (Vapors) Waste Gas Amounts H M L

5 Metal Processing Atmospheres – Similar Constituents  Carburizing, Carbonitriding, FNC & Nitriding  N 2, CO, H 2, CO 2, H 2 O, CH 4, O 2, NH 3, CH 3 OH  Atmosphere Tempering and Annealing  N 2, H 2, CO, CO 2, H 2 O, CH 4, O 2, NH 3, Ar  Steel, Copper and Aluminum Brazing  N 2, H 2, CO, CO 2, H 2 O, CH 4, O 2, NH 3, Ar  Powdered Metal Sintering and Annealing  H 2, N 2, CO, CO 2, H 2 O, CH 4, O 2, NH 3, H 2 S

6 Typical Atmosphere Control - Measures Only One Gas Species  Types  Zirconia Oxygen Probe – Measures Oxygen  Dew Point Meters – Measures Water Vapor  Electrochemical Cells – Low Range Single Gases  Benefits  Proven Technology  Lower Capital Cost  Low Complexity  Disadvantages  Other Gas Constituents Assumed (Guessed)  Assumptions Often Wrong  Limits Process Control & Improvement Options  Requires High Process Atmosphere Flows

7 Improved Atmosphere Control – Single Gas Plus Infra-Red  Economically Measures Three More Gases  Carbon Monoxide  Carbon Dioxide  Methane  Benefits  Proven Technology and Vendors  Can be Used to Reduce Atmosphere Use  Disadvantages  Cannot Measure Hydrogen, Nitrogen and Inerts  Expensive to Measure Other Significant Gases  Limited Measurement Range  Requires Frequent Calibration  Limits High Efficiency Atmosphere Gas Mixtures  Can’t Significantly Reduce Atmosphere Use

8 Other Gas Analysis Technologies – Less Applicable to Atmospheres  Gas Chromatography (GC)  High Installed Capital Cost ($15,000 - $60,000)  Slow (2 Minutes+)  Complex – Use Requires Training  Carrier Gas and Frequent Calibration  Few Used for Atmosphere Control  Mass Spectroscopy (MS)  Higher Installed Capital Cost ($50,000 - $120,000)  Best Applied on Vacuum Processes  Ionizer Susceptible to Water Damage  Expensive to Maintain  Many Gases Hard to Determine (Equal Charge-Mass)

9 Atmosphere Control Goal – High-Rate Complete Gas Analyzer  Measure All Reactive Gases  Monitor Any Industrial Atmosphere  Fast Analyzer Response  Compact and Operator Friendly  Rugged, Reliable, Easy to Service  Minimal Calibration  Cost-Effective  Allows Advanced Atmosphere Control

10  Unique Frequency “Shift” for Each Chemical Bond  Little Interference Between Most Gases  Measures Gases of All Types (Except Inerts)  Rapid “Real Time” Response Rates Possible  Signal Directly Proportional to Number of Gas Atoms  PPM-100% Gas Concentrations with One Detector  Resolution and Accuracy Depends On:  Laser Power and Optics Variation  Gas Concentration and Pressure  Molecular Bond Type  Background and Scattered Radiation  Optical and Electronic Detector Circuitry Laser Raman Gas Spectroscopy - Features

11 Core of Laser Gas Control – Unique 8 Gas Detector Mirror Polarizer Prism & Mirror Laser Beam Gas Sample Tube Gas Out 8 Optical Filters/Sensors (1 for Each Gas Measured) Detector Assembly Gas Out Special Particle Filter Plasma Cell Gas to be Analyzed In

12 Laser Gas Detector Module – Features  Low Power Laser Insures Safety  Sample Gas Flows Analyzed Inside Instrument for Higher Inherent Accuracy  Discrete Optical Filtering and Quantifying  8 Gases Detected – Can be Process Specific  Simultaneous Detection of Each Gas Species  Fast Detector Response (50 milliseconds)  Array Based Interference Computations  Most Cost-Effective Approach

13 Standard Furnace Constituents Monitored and Detection Limits Gas SpeciesLower Limit Hydrogen - H ppm* Nitrogen - N 2 50 ppm Oxygen - O 2 50 ppm Water Vapor - H 2 O10-50 ppm* Carbon Monoxide - CO50 ppm Carbon Dioxide - CO 2 25 ppm Organics - C x H y ppm* Ammonia - NH ppm* *Customer Selectable – Selecting Lower Value Limits The Upper Range to 30%; Other Gas Species Optional

14 Gas Analyzer – Subsystem View Detector Assembly Integrated Computer & Control System Sample Pump, Valves and Pressure Control

15 Subsystem Features  Integrated Sampling and Calibration System  Internal Pump and Valves  Low Volume Sample Gas Flows (200 ml/minute)  Multiple Sample Port Options  Automated Zero and Span Calibration  Automated Sample Line Monitoring (Flow & Pressure)  Integrated Electronics & Software  Pentium III Computer w/ HMI and Data Trending  Customizable Process Deviation Analysis  Local and Remote Displays and Interfaces  OPC Server and Client for Connectivity  Available Analog and Digital I/O Options  Multiple Configurable Process and PLC Interfaces  NeSSI Compatible

16 Example Main Control Screen

17 Mobile Furnace Process Control – 4 Samples, 8 Pressures, 8 Temperatures  Furnace Tuning & Commissioning  Furnace Performance Problem Resolution  Advanced Atmosphere Demonstration and Testing  ARI/APCI Consulting Service

18 Advanced Carburizing Control – 2 Batch Furnaces Inside View Outside View

19 Analyzer/Controller – 16 Zone Continuous Furnace Inside View Outside View

20 Current Product Integrates Sampling System & Added Features  Fully Integrated Sample System (1-16 Ports)  “Real Time” On-Line Monitoring and Control (1 to 15 Second to Update Each Sample Location)  Operates with Existing PLCs and Sensors  Low Volume Sample Gas Flows (200 ml/minute)  Electronic Flow and Pressure Monitoring  Optics Protection and Enclosure Inerting  Sample Line Pre-Purge and Back-flush Options  Automatic Condensate Removal  Precision Temp. Controlled NEMA Enclosures  Self-Monitoring of Critical Functions  Many Wired and Wireless Communication Options

21 Economic Benefits of Laser Gas Atmosphere Analysis and Control  Multiple Gas Analysis Capability = System Versatility  Economic Paybacks in Many Ways  Reduce Energy Costs  Increase Production Capacity  Improve Component Quality  Improve Component Consistency  Reduce Destructive Analysis Costs  Reduce Re-Work Costs  Better Process Documentation  Maintenance Early Warnings  Enhanced Furnace Safety Depends on System FunctionsUsed

22 Rapid Carburizing and Atmosphere Recovery Demonstrated at Dana

23 System Location in Plant “Explosion Resistant” Test Area “Explosion Resistant” Test Area

24  Improves Steel Wear Resistance on Part Surfaces  Maintains Steel “Toughness” at Part Depth  Parts Heated in a Gas “Atmosphere”  Atmosphere Provides Reactive Chemistry Typical Parts (Gears) Typical Furnace (Batch) Carburizing Use & Purpose

25 Traditional Carburizing Atmosphere Endogas Air Natural Gas Composition: CO~20%, N 2 ~39%, H 2 ~39%, 1% CH 4, Balance: CO 2, H 2 O, O 2 At Metal Surface: 2H 2 +2CO+3Fe  Fe 3 C+2H 2 O+CO 2 3Fe+CH 4  Fe 3 C+2H 2 Exhaust Stack

26 Typical Carburizing Operation (Slow - Approaches Equilibrium)

27 Benefits of Laser Gas Analysis - Conventional Heat Treating  Atmosphere Gas Consumption Reduced Endothermic Example – 90%+ Exothermic Example – 50%+  Extra Gas Generators Turned Off  Shorter Cycle Times Inherent Carburizing Example – Up to 20%  Process Energy Savings Significant Carburizing Example – 25% of Total Furnace Use Exothermic Example – 15% of Total Furnace Use

28 Example 96% Endo Savings Surface Combustion All-Case Furnace (Shown Under Standard Operation) Stack and Flare Shut Off Door and Burner Leaks Reduced

29 Initial Demonstration – Atmosphere Recovery Process IR-GC First - Later Laser Gas Analyzer

30 Atmosphere Recovery – Prototype System  Prototype Development, Assembly and Testing  First Full Scale Operation - Aug. 6, 1997  Finding - Process Worked and Increased Productivity IR-GC (Later Replaced by Laser Analyzer)

31 ARI Effluent Control System Detector Module & Controller Sampling System (Composition, Pressure & Temperature) ARI Pressure Control & Safety System Furnace Chamber Vestibule Existing PLC Furnace Control Existing Over Temperature Controller Burner Valves Existing N2 Safety System Gas CGas BGas A Calibration Gases Sample gas and pressure line(s) plus optional temperature probe(s) Furnace Atmosphere Supply Existing Batch Furnace Bulk N 2 Natural Gas for Burners Existing IRI Gas Train O 2 Probe KEY: Control Signals Burner Natural Gas ARI Rapid Carburizing Process Control Diagram ARI Flow Monitoring & Control Assembly ARI Laser Gas Analyzer Calibration Gases

32 Example Rapid Carburizing Trial

33 Benefits of Laser Gas Control – In-Situ Rapid Carburizing (Non-Equilibrium)  Greatly Increased Production Capacity Example: Cycle time for ~1mm case reduced 50%  Up to 40% Energy Savings  Elimination of Endo Generators  Further Improved Product Quality  Reduced Sooting and Furnace Maintenance

34 System Paybacks in Less Than 12 Months * Includes Furnaces, Atmosphere Generators, and Ancillary Equipment if Plant New or Near Capacity Benefit Standard Carburizing Rapid Carburizing Exothermic Annealing Productivity Improvement Reduced Processing Times Improved Quality Up to 20%Up to 50% Reduced Energy Consumption25%40%Up to 30% Reduced Process Gas UseUp to 90%Up to 98%Up to 90% Reduced Regulated EmissionsOver 90%Over 98%Over 90% System Price (Typical)$40-100K$70-150K$40-90K Example Customer Gear Manufacturer Axle Manufacturer Non-Ferrous Annealer Cost Benefits Capital Savings (Avoiding Conventional Equipment)* Operation & Maintenance Cost Reduction $150K $100K/year $250K $200K/year $90K $100K/year

35 Rapid Carburizing – Metallurgical Findings Summary  Batch Cycle Times Faster (Load to Unload)  Same Process Temperature (Typically 1750 Deg. F.)  Case Depth of.040” – 35% to 50% Faster  Case Depth of.065 – 20-30% Faster  Less Case Depth Variation Though the Load  Controllable Carbon Content/Hardness Profile  Controllable Retained Austenite Levels  Controllable Iron Carbide Levels  Wide Variation in Atmosphere Constituents Tolerated  Soot Control Algorithms Do Not Affect Parts  All Parts Released for Production

Significant Process Industries - Gas Based  Metal Processing – Initial Success  Automotive & Aerospace Heat Treating  Metal Refining & Powdered Metal  Many Others – Ready for Trials  Bio-Pharma  Petrochemical  Semiconductor  Energy Utilities  Glass & Ceramic  Continuous Emission Monitoring

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